MX2014005024A - Thickener containing at least one polymer based on associative monomers and which can be obtained by inverse emulsion polymerization. - Google Patents

Abstract

The invention relates to a thickener which can be obtained according to a method, characterized in that a polymer is obtained by an inverse emulsion polymerization of a) at least one water-soluble ethylenically unsaturated monomer comprising at least one anionic monomer and/or at least one non-ionic mononer, b) at least one ethylenically unsaturated associative monomer, c) optionally at least one cross-linking agent, d) optionally at least one chain transfer agent. The temperature is kept constant during the inverse emulsion polymerization and is at least 40 °C, preferably between 50 - 90 °C, and the activator is added after the inverse emulsion polymerization in order to obtain the thickness.

Description

THICKNESS CONTAINING AT LEAST ONE POLYMER BASED ON ASSOCIATIVE MONOMERS AND THAT CAN BE OBTAINED BY POLYMERIZATION IN REVERSE EMULSION Description The present invention relates to a thickener that can be prepared by a process in which a polymer is prepared by inverse emulsion polymerization at a constant temperature of at least 40 ° C. During reverse emulsion polymerization, the components used are at least one ethylenically unsaturated, water-soluble monomer comprising at least one anionic monomer and / or at least one non-ionic monomer, and at least one ethylenically unsaturated associative monomer . Furthermore, the present invention relates to a process for producing the thickener according to the invention and also surfactant-containing formulations comprising at least one thickener. The invention further provides the use of the surfactant-containing formulation, for example as a softener or as a liquid detergent, and also the use of the thickener, for example as a viscosity modifier.

WO 03/102043 relates to aqueous formulations comprising a cationic polymer prepared from (i) an ethylenically monomer unsaturated, soluble in water or a mixture of monomers comprising at least one cationic monomer, (ii) at least one interleaver in an amount of more than 50 ppm based on component (i), and (iii) at minus a chain transfer agent. Aqueous formulations can be used as thickeners in household formulations.

Document O 2009/019225 relates to an aqueous dispersion of an alkali-soluble copolymer, which is suitable as an associative thickener. The copolymer comprises polymerized units of a) at least one ethylenically unsaturated carboxylic acid, b) at least one non-ionic ethylenically unsaturated surfactant monomer, c) at least one Ci-C2 alkyl methacrylate and d) at least one a C2-C4 alkyl acrylate, wherein the alkyl chain length averaged over the alkyl group number of the alkyl acrylate is 2.1 to 4.0. The associative thickeners can be prepared by emulsion polymerization. The associative thickeners are suitable for use in detergents and cleaners.

The compositions of Liquid Dispersion Polymer (LDP) are described in WO 2005/097834. These LDP compositions comprise a hydrophilic, water-soluble or water-swellable polymer with a neutralization content of about 25 to about 100%, a non-aqueous vehicle phase and a surfactant of oil in water. The hydrophilic, water-soluble or water-swellable polymer is preferably obtained by polymerization, for example, of acrylic acid or methacrylic acid. LDP dispersions are suitable for the production of microparticulate thickeners, as used, for example, in aqueous or organic compositions, in particular in personal care or pharmaceutical formulations.

WO 2010/078959 relates to cationic polymer thickeners consisting of an interlaced, water swellable cationic polymer comprising at least one cationic monomer and optionally nonionic or anionic monomers, wherein the polymer comprises less than 25% polymer chains soluble in water, based on the total weight of the polymer. In addition, the polymer comprises an interlayer at a concentration of 500 to 5000 ppm relative to the polymer. The cationic polymer is prepared by reverse emulsion polymerization.

WO 2010/079100 describes fabric softening compositions comprising polymers according to WO 2010/078959.

US 2008/0312343 relates to inverse latex compositions and their use as a thickener and / or emulsifier, for example for the production of cosmetic or pharmaceutical formulations. The inverse latex compositions comprise at least 50 to 80% by weight of at least one linear, branched or entangled organic polymer (P), at least 5 to 10% by weight of a water-in-oil type emulsifier system, 5 to 45% by weight of at least one oil and up to 5% by weight % of water. The polymer P comprises neutral monomers and optionally cationic or anionic monomers. The reverse latex composition may optionally comprise up to 5% by weight of an emulsifier system of the oil-in-water type. The inverse latex compositions can be prepared by inverse emulsion polymerization.

EP-A 172 025 relates to a dispersion in a continuous liquid phase of a polymer, which is formed by polymerization of an ethylenically unsaturated monomer comprising a hydrophobic group of at least 8 carbon atoms and a copolymerizable ethylenically unsaturated monomer with the same. The dispersion is stable and essentially anhydrous, and comprises at least 40% by weight of polymer. During the polymerization, anionic monomers, for example, can be used as an ethylenically unsaturated, copolymerizable monomer. The polymerization can be carried out as a reverse emulsion polymerization.

EP-A 172 724 relates to polymers which are prepared by copolymerization of a) an ethylenically unsaturated monomer comprising a hydrophobic group with at least 8 carbon atoms and b) water-soluble ethylenically unsaturated monomers. All the soluble monomers as a mixture in water, and the polymer is prepared by inverse emulsion polymerization. The polymer particles have a dry size of < 4 pm As monomer component b) it is possible to use anionic monomers such as acrylic acid in the form of the free acid or as a water soluble salt, and also nonionic monomers such as acrylamide.

"EP-A 172 723 relates to a process for flocculating a suspension using an essentially linear, water-soluble polymer with a" single-point intrinsic viscosity "of > 3. The polymer is a two or more copolymer. more ethylenically unsaturated monomers comprising at least 0.5% by weight of a monomer, comprising hydrophobic groups The polymer can also be a cationic polymer.

The problem on which the present invention is based consists in providing novel thickeners. The object is achieved by means of the thickeners according to the invention which can be prepared by a process in which a polymer is obtained by inverse emulsion polymerization. a) at least one ethylenically unsaturated monomer, soluble in water, comprising at least one anionic monomer and / or at least one non-ionic monomer, b) at least one ethylenically unsaturated associative monomer, c) optionally at least one interleaver, d) optionally at least one chain transfer agent, wherein the temperature during the inverse emulsion polymerization is kept constant and is at least 40 ° C, preferably 50 to 90 ° C, and when the inverse emulsion polymerization is complete, the activator is added to obtain the thickener.

The thickeners according to the invention are characterized in that they have advantageous properties with respect to deposition, shear thinning, stabilization and / or viscosity (thickening). By deposition is meant the deposition of the active ingredients of, for example, a fabric softener on a fiber during a washing operation. Applied to the present invention, this means that, for example, a thickener according to the invention comprising at least one polymer (active ingredient) is present in a fabric softener and the fabric softener is used during or after the washing operation. The thickeners according to the invention promote this deposition of the active ingredient during or after the washing operation to a considerable degree. Particularly good properties with respect Deposition can be achieved when using polymers that are based on at least one associative monomer, a nonionic monomer such as acrylamide, and optionally an anionic monomer.

When evaluating the shear dilution, it is important that the thickener or fabric softener corresponding in its basic state, be viscous and thick while under agitation. Improved shear thinning has a positive effect on the life and properties of pumps during the production of fabric softener, promotes convenient dosing for the consumer and promotes the free use of fabric softener residues, especially in washing machines that have an automatic dosing device. The thickeners according to the invention improve the stability of the thickener as such and that of the corresponding formulation. The sedimentation or migration of particles is effectively avoided, regardless of whether they are in the order of magnitude of nanometers, microns or millimeters. A contributing factor here is the advantageous deformation point of the thickener according to the invention. Moreover, it has the advantage that any required redispersion and thickening are achieved very quickly.

The thickeners according to the invention in which a mixture of at least two activators is present, wherein at least one activator has a high HLB value and at least one activator has a low HLB value, they are associated with an additional advantage. The combination of said mixture of activators with polymers comprising at least one building block of ethylenically unsaturated associative monomer leads to spontaneous phase inversions (within seconds) under dilution of a thickener with water, without requiring an additional energy input, for example in the form of agitation.

Furthermore, in the case of the thickeners according to the invention, it is advantageous if the ratio of associative monomer to total polymer is relatively low. When the thickener is used in formulations containing surfactant, the effect of the associative monomers is optimal even in amounts of about 0.5% by weight (based on the polymer).

A further advantage is considered to be that the polymer of the thickener according to the invention is prepared by reverse emulsion polymerization in which the temperature is kept constant at at least 40 ° C as a result of which a good uniformity of distribution of The associative monomer building blocks within the polymer are observed. Particularly in the case of using small amounts of, for example, 0.1 to 1% by weight of associative monomers, this is advantageous with with respect to the aforementioned global rheological properties such as thickening, shear thinning, stabilization, and also wash and rinse effects.

The embodiments of the present invention in which the polymers present in the thickener are prepared using little or no interlacing are also associated with advantages. ? Because of the relatively high soluble (in water) components of the polymer, re-fouling during a washing operation is reduced. Consequently, the article to be washed, even after repeated washing processes, has clean fibers that have been effectively freed from dirt particles, which means that no smudging is detected. No adhesion and / or redistribution of dirt particles / very light polymers is observed in the washed articles.

Within the context of the present invention, definitions such as C 1 -C 30 alkyl, as defined, for example, below for the radical R 9 in formula (I), means that the substituent (radical) is an alkyl radical which it has a number of carbon atoms from 1 to 30. The alkyl radical can be either linear or branched and also optionally cyclic. Alkyl radicals having both a cyclic and a linear component also fall within this definition. The same also applies to other alkyl radicals, such as, for example, C 1 -C 4 alkyl radical or Ci 6 -C 22 alkyl radical. The alkyl radicals may optionally also be mono- or polysubstituted with functional groups such as amino, quaternary ammonium, hydroxy, halogen, aryl or heteroaryl. Unless otherwise indicated, the alkyl radicals preferably have no functional group as a substituent. Examples of alkyl radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 2-ethylhexyl, tertiary butyl (tert-Bu / t-Bu), cyclohexyl, octyl, stearyl or behenyl.

The present invention is described in more precise terms below.

First, the monomer components that are used for the preparation of the polymer present in the thickener according to the invention are defined in more detail. The inverse emulsion polymerization process as such for producing the polymer and the thickener according to the invention comprising at least one polymer and also additives or auxiliaries optionally used in the reverse emulsion polymerization and / or the thickener production processes they are defined in more detail later.

The thickener according to the invention comprises at least one polymer which is obtained by reverse emulsion polymerization of the following components a) and b) and optionally also c) and d).

As component a), at least one ethylenically unsaturated, water-soluble monomer comprising at least one anionic monomer and / or at least one non-ionic monomer is used. The anionic and nonionic monomers as such are known to those skilled in the art.

If at least one anionic monomer is present in component a), it is preferably selected from acrylic acid, methacrylic acid, itaconic acid, maleic acid or a salt thereof, in particular, the anionic monomer is Na acrylate.

If at least one non-ionic monomer is present in component a), apart from the nitrogen-containing monomers described below, such as, for example, the compounds according to formula (I), the anionic monomers described previously they are also suitable as nonionic monomers. Said nonionic monomers are preferably the methyl or ethyl esters of acrylic acid or methacrylic acid such as ethyl acrylate or methyl acrylate. Preference is also given to the corresponding dimethylamino-substituted esters such as (meth) dimethylaminoethyl acrylate.

Preferably, the nonionic monomer is selected from N-vinylpyrrolidone, N-vinylimidazole or a Composed in accordance with formula (I) where R7 is H or C1-C4 alkyl, R8 is H or methyl, and R9 and RIOA independently of each other, are H or Ci-C30 alkyl.

The nonionic monomer is in particular preferably acrylamide, methacrylamide or dialkylaminoacrylamide.

In a preferred embodiment of the present invention, in the polymer, component a) comprises 30 to 99.5% by weight of at least one anionic monomer and 0.5 to 70% by weight of at least one nonionic monomer.

In a further preferred embodiment of the present invention, component a) comprises 100% by weight of at least one nonionic monomer.

In a further preferred embodiment of the present invention, component a) comprises 100% by weight of at least one anionic monomer.

Furthermore, within the context of the present invention, it is preferred that component a) does not comprise cationic monomer.

As component b), at least one ethylenically unsaturated associated monomer is used in the reverse emulsion polymerization to produce the polymer. The associative monomers as such are known to one skilled in the art. Suitable associative monomers are described, for example, in the document. Or 2009/019225. The associative monomers are also referred to as surfactant monomers.

Preferably, in the polymer, the ethylenically unsaturated associative monomer according to component b) is selected from a compound according to formula (II) R-0- (CH2-CHR '-0) n-CO-CR "= CH2 (II) wherein R is C6-C50 alkyl, preferably C8_C3o alkyl, in particular Ci6-C22 alkyl, R 'is H or C1-C4 alkyl, preferably H, R "is H or methyl, n is an integer from 0 to 100, preferably 3 to 50, in particular 25.

As component b), particular preference is given to using a compound according to formula (II) in which R is Ci6-C22 alkyl, R 'is H, R "is H or methyl and n is 25 The compounds according to formula (II) are commercially available in solution, for example under the name Plex 6954 0 of Evonik Rohm GmbH. These are methacrylates of fatty alcohol ethoxylates. A suitable fatty alcohol ethoxylate is, for example, the commercially available Lutensol® AT 25 (BASF SE, Ludwigshafen, Germany).

The radical R in the compounds according to the formula (II) can also be present as a mixture of radicals with different chain lengths, such as i6 and Cie. An example of these is Ci6 ~ Ci8 (ethylene glycol) fatty alcohol methacrylate ether, wherein both Ci6 and Ci8 fatty alcohol radicals (in non-negligible amounts) are present as a mixture. In contrast to this, for example, in the compounds (according to formula (II)) of behenyl-25-methacrylate and cetyl-methacrylate-25, the respective radical R is not present as a mixture but as a C22 chain or Ci6. Other chain lengths occur only in the form of impurities. The number "25" in these compounds according to formula (II) represents the size of the variables n.

In the preparation of the polymer by inverse emulsion polymerization, at least one interleaver may optionally be present as component c). Suitable interleavers are known to the person skilled in the art. Preferably, in the polymer, the crosslinker according to component c) is selected from divinylbenzene; tetraallylammonium chloride; allyl acrylates; allyl methacrylates; diacrylates and dimethacrylates of glycols or polyglycols; butadiene; 1,7-octadiene, allyl acrylamides or allylmethacrylamides; bisacrylamidoacetic acid; N, N'-methylenebisacrylamide or polyallyl polyol ethers such as polyallyl sucrose triallyl ether or pentaerythritol. Also suitable as a preferred interleaver is dialkyldimethylammonium chloride.

In addition, during the preparation of the polymer by inverse emulsion polymerization, at least one chain transfer agent can be used as component d). Suitable chain transfer agents are known to the person skilled in the art. Preferred chain transfer agents according to component d) are selected from mercaptan, lactic acid, formic acid, isopropanol or hypophosphites.

Preferably, in the thickener according to the invention, at least one polymer is present which can be prepared by reverse emulsion polymerization of a) 20 to 99.99% by weight, preferably 90 to 99.95% by weight (based on the polymer) , of at least one ethylenically unsaturated monomer soluble in water comprising at least one anionic monomer and / or at least one non-ionic monomer, b) 0.01 to 80% by weight, preferably 0.05 to 5% by weight, particularly preferably 0.1 to 1% by weight (based on the polymer) of at least one ethylenically unsaturated associative monomer, c) 0 to 0.3% by weight, preferably 0.01 to 0.1% by weight (based on the polymer) of optionally at least one interleaver, d) 0 to 0.3% by weight, preferably 0.01 to 0.1% by weight (based on the polymer) of optionally at least one chain transfer agent.

In a further embodiment of the present invention, the water-soluble fractions of the polymer are more than 25% by weight (based on the total weight of the polymer), particularly when little or no interlayer is used in addition to the associative monomer. Preferably, more than 40% by weight, in particular 70 to 100% by weight, of the polymer is soluble in water. The solubility of the polymer is determined by methods known to the person skilled in the art, the polymer present in the thickener according to the invention being mixed with a defined amount of water (see, for example, EP-A 343 840 or preferably the method of determination of the sedimentation coefficient in the Svedberg unit (sved) according to P. Schuck, "Size- distribution analysis of macromolecules by sedimentation velocity ultracentrifugation and Lamm equation modeling, Biophysical Journal 78, (3) (2000), 1606-1619).

Preferably, in this embodiment, the crosslinker fraction (component c) used in the reverse emulsion polymerization of the polymer is < 10% by weight (based on the total amount of components a) a d)). It is particularly preferred not to use any interlayer in the reverse emulsion polymerization of the polymer.

The thickener according to the invention comprises at least one activator as an additional component. Activators as such are known in principle by the person skilled in the art. Suitable activators are preferably surfactants, for example anionic, nonionic, cationic and / or amphoteric surfactants, which are described, for example, in WO 2009/019225. Preference is given to using anionic and / or nonionic surfactants.

The nonionic surfactants used are preferably fatty alcohol alkoxylates. The fatty alcohol alkoxylates are also referred to as polyalkylene glycol ethers. Preferred fatty alcohol alkoxylates are alkoxylated alcohols, advantageously ethoxylated, in particular primary alcohols preferably having 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or branched, preferably 2-methyl-branched, or can comprise linear and methyl-branched radicals in a mixture, as they are usually present in oxo alcohol radicals. However, especially preferred are alcohol ethoxylates with linear radicals of alcohols of natural or technical origin having 12 to 18 carbon atoms, for example coconut alcohol, palm tree spirit, tallow fatty alcohol or oleyl alcohol - or mixtures of them, as can be derived, for example, from castor oil - and on average 2 to 8 EO per mole of alcohol. Preferred ethoxylated alcohols include, for example, Ci2-Ci4 alcohols with 3 EO, 4 EO or 7 EO, C9-Cn alcohol with 7 EO, C13-C15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO , Ci2-Ci8 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C12-C14 alcohol with 3 EO and Ci2-Ci8 alcohol with 7 EO. The established degrees of ethoxylation are average statistical values that can be an integer or a fraction for a specific product. The preferred alcohol ethoxylates have a narrow homologous distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples thereof are tallow fatty alcohols with 14 EO, 25 EO, 30 EO or 40 EO. It is also possible to use nonionic surfactants comprising EO and PO groups together in the molecule. Here, it is possible to use block copolymers with block units EO-PO or block units P0-EO, but also copolymers of EO-PO-EO or copolymers of P0-EO-PO. Of course it is also possible to use mixed alkoxylated nonionic surfactants in which the EO and PO units are not in the form of blocks, but in random distribution. Said products can be obtained by simultaneous action of ethylene oxide and propylene oxide in fatty alcohols.

In addition, alkyl glucosides or alkyl polyglucosides can also be used as additional nonionic surfactants. For alkyl glucosides and alkylpolyglucosides, the person skilled in the art understands compounds which are formed by at least one alkyl fragment and at least one sugar or polyazugar fragment. The alkyl fragments are preferably derived from fatty alcohols with a carbon number of 12 to 22, and the sugar fragments are preferably derived from glucose, sucrose or sorbitan.

For example, the alkyl glycosides of the general formula (1) R10 (G) x (1) can be used, in which R1 is a straight or methyl-branched straight chain aliphatic radical, in 2-methyl-branched, having 8 to 22, preferably 12 to 18, carbon atoms, and G is a glucoside unit having 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, which specifies the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

An additional class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated fatty acid esters, preferably ethoxylated or ethoxylated and propoxylated, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular methyl esters of fatty acid, as described, for example, in Japanese patent application JP 58/217598, or which are preferably prepared by the process described in the application of international patent WO-A-90/13533.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-, N-dimethylamine oxide and N-tallowalkyl-N, -dihydroxyethylamine oxide, and the type of fatty acid alkanolamide can also be used. The amount of these nonionic surfactants is preferably not greater than that of the ethoxylated fatty alcohols, in particular not more than half of them.

Additional suitable surfactants are polyhydroxy fatty acid amides of the formula (2), wherein R2C (= 0) is an aliphatic acyl radical having 6 to 22 carbon atoms, R3 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine, and subsequent acylation with a fatty acid, an alkyl fatty acid ester or a fatty acid chloride .

The group of the polyhydroxy fatty acid amides also includes compounds of the formula (3) wherein R 4 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 5 is a linear, branched or cyclic alkylene radical having 2 to 8 carbon atoms or an arylene radical having 6 to 8 carbon atoms, and R6 is a linear, branched or cyclic alkyl radical, or an aryl radical, or an oxyalkyl radical having 1 to 8 carbon atoms, wherein the Ci-C4 alkyl or phenyl radicals are preferred, and [ Z] 1 is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical. [Z] 1 is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be converted to the desired polyhydroxy fatty acid amides, for example, in accordance with document OA-95/07331 by reaction with fatty acid methyl esters in the presence of a alkoxide as a catalyst.

The anionic surfactants used are, for example, those of the sulfonate and sulfate type. Suitable surfactants of the sulfonate type here are alkylbenzene sulphonates, preferably C9-C13 alkylbenzene sulphonates, olefin sulphonates, ie mixtures of alken- and hydroxyalkanesulfonates, and disulfonates, as obtained, for example, from C12-C18 monoolefins with double terminal or internal bonds by sulfonation with gaseous sulfur trioxide and alkaline or acid hydrolysis subsequent sulfonation products. Also suitable are alkanesulphonates, preferably secondary alkane sulphonates, which are obtained, for example, from C12-C18 alkanes by sulfodoration or sulfoxidation with subsequent hydrolysis or neutralization. Esters of fatty acids a-sulfo (ester sulfonates), for example the methyl-sulphonated esters of hydrogenated coconut fatty acids, palm kernel fatty acids or tallow fatty acids, are also suitable.

Additional suitable anionic surfactants are glycerol esters of sulfated fatty acid. Fatty acid glycerol esters are mono-, di- and triesters, and mixtures thereof, as obtained during the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3. to 2 moles of glycerol. Preferred sulfated fatty acid glycerol esters are sulfation products of saturated fatty acids having 6 to 22 carbon atoms, for example of caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or acid behenic Additional suitable anionic surfactants are fatty alcohol sulfates, for example alk (en) yl sulfates. Sulfates of alkyl (en) yl preferred are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of the C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol, or of the oxo alcohols of C 10 -C 20 and those monoesters of secondary alcohols of these chain lengths. In addition, the preferred alkyl (en) yl sulfates of said chain lengths comprising a straight chain straight alkyl radical produced on a petrochemical basis, having degradation behavior analogous to equivalent compounds based on fatty chemical starting materials. In the interest of washing technology, C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates, and also C 14 -C 15 alkyl sulfates are preferred. Also, the 2,3-alkyl sulfates, which are prepared, for example, in accordance with the patent specifications of E.U.A. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN®, are suitable anionic surfactants.

The monoesters of sulfuric acid of the ethoxylated C7-C21 straight-chain or branched alcohols with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched Cg-Cu alcohols with an average of 3.5 moles of ethylene oxide (EO) or fatty alcohols of C i2 -C1 8 with 1 to 4 EO, They are also suitable.

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or esters of sulfosuccinic acid, and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates comprise Cs-Cis fatty alcohol radicals or mixtures thereof. Particularly, the preferred sulfosuccinates comprise a fatty alcohol radical which is derived from ethoxylated fatty alcohols. In connection with this, particular preference is given in turn to sulfosuccinates whose fatty alcohol radicals are derived from ethoxylated fatty alcohols with narrow homolog distribution. Also, it is also possible to use alky (en) ilsuccinic acid having preferably 8 to 18 carbon atoms in the alkyl (en) yl chain or salts thereof.

Additional suitable anionic surfactants are alkyl carboxylates, for example the sodium salts of saturated or unsaturated fatty acids, wherein the alkyl radical of the alkyl carboxylate is preferably linear.

Within the context of the present invention, the activator is preferably selected from alkoxylates of fatty alcohol, alkyl glucosides, alkylcarboxylates, alkylbenzene sulfonates, secondary alkan sulfonates and fatty alcohol sulfates, in particular preferably selected from fatty alcohol alkoxylates. An example of a preferred fatty alcohol alkoxylate is poly (3-6) ethoxylate (secondary) of C6_Ci7.

Furthermore, it is preferred, within the context of the present invention, to use an activator having a (relatively) high HLB (hydrophilic-lipophilic balance) value. Preferably, the activator preferably has an HLB value of from 7 to 18, most preferably from 8 to 15 and particularly preferably from 9 to 13.

Activators with a high HLB value are preferably i) fatty alcohol alkoxylates formed from secondary alcohols or mixtures of alcohols having 12 to 18 carbon atoms and ethylene oxide or propylene oxide, and ii) alkyl glucosides formed from of sucrose and C8-C22 fatty alcohols. Examples of such activators are the commercially available Synperonic 87K from Croda GmbH Herrenpfad-Süd 33, 41334 Nettetal, Germany; Croduret 40 or other ethoxylated hydrogenated castor oils (ricinus oils) such as Etocas 40 or Crodesta F110, all from Croda.

In a further embodiment of the present invention, it is preferred to use a mixture of at least two activators, wherein at least one activator has a high HLB value and at least one activator of a low HLB value. The activator with a high HLB value preferably has a HLB value of > 12 to 20, and the activator with a low HLB value preferably has a HLB value of 1 to 12. In this embodiment, the activator with a high HLB value and the activator with a low HLB value can be present in one with the other in any desired relationship known to one skilled in the art. Preferably, 20 to 50% by weight of activator with high HLB value and 50 to 80% by weight of activator with a low HLB value are used in the mixture. Furthermore, preferably, this ratio of activator with high HLB value for the activator with a low HLB value is adjusted in such a way that the overall HLB value is from 7 to 18, most preferably from 8 to 15 and in paular preferably from 9 to 15. to 13.

In these mixtures of at least two activators, activators with a high HLB value used are preferably alkyl glucosides or polyalkyl glucosides or polyalkyloligoethylene oxide glucoside based on sucrose or sorbitan and C8 to C22 fatty alcohols, such as polyethylene glycol sorbitan monostearate or monostearate polyoxyethylene sorbitan. Examples of such activators are commercially available Crillet 1, Crillet 3 or Crodesta F160, all available from Croda. As activators with a low HLB value, preference is given to the use of alkyl glycosides formed from sucrose or sorbitan and Ce to C22 fatty alcohols or fatty acids, such as sorbitan laurate or sorbitan stearate. Examples of such activators are the commercially available Crill 1, Crill 3 or Crodesta FIO from Croda.

Within the context of the present invention, the ratio of activator to polymer can be adjusted within any desired values known to the person skilled in the art. Preferably, the ratio of activator to polymer is > 10: 100 [% by weight /% by weight], most preferably 10.5 to 50: 100 [% by weight /% by weight], paularly preferably 11.5 to 20: 100 [% by weight /% by weight].

In the thickeners according to the invention, other components may be present in addition to the polymer and the activator. Suitable additional components are defined in more detail in the following text in the context of the preparation of the thickener and the polymer. Suitable additional components can be, for example, oils and solvents.

In the thickener according to the invention, the polymer may be present dispersed in the oil phase, in dispersed form, preferably as a reverse dispersion, dispersion of water in oil, or as an anhydrous polymer dispersed in oil.

Within the context of the present invention, the polymer is prepared by emulsion polymerization. The reverse emulsion polymerization is as such known to one skilled in the art. By inverse emulsion polymerization, the person skilled in the art understands, in general, the polymerization processes according to the following definition: the hydrophilic monomers are dispersed in a hydrophobic oil phase. The polymerization takes place directly in these hydrophilic monomer pales by the addition of initiator.

Furthermore, within the context of the present invention, the temperature during the inverse emulsion polymerization is kept constant, the temperature being at least 40 ° C, preferably 50 to 90 ° C. Normally, the upper temperature limit of 150 ° C is not exceeded during inverse emulsion polymerization.

If, within the context of the present invention, the temperature is kept constant during a reverse emulsion polymerization, this means that from the beginning of the inverse emulsion polymerization the temperature is maintained at a constant value. Fluctuations of +/- 5 ° C, preferably +/- 2 ° C and especially +/- 1 ° C during the polymerization process are considered as a constant temperature (based on the desired constant temperature value). The temperature is maintained constant until the reverse emulsion polymerization is complete; preferably, this is the case after a conversion of more than 90% of the monomers used, most preferably more than 95% by weight and particularly preferably in the case of complete conversion (100% by weight). The temperature can be kept constant by removing the heat of reaction that is produced by cooling. The beginning of the polymerization is usually the addition of the polymerization initiator, preferably the addition of a redox initiator system. Normally, the system is first heated to the desired temperature and a constant temperature is maintained while stirring. Then, the polymerization initiator is added, as a result of which the polymerization process begins. In one embodiment of the present invention, the temperature is kept constant at a value above the melting point of the associative monomer used.

When the reverse emulsion polymerization is complete, the activator is added to the polymer (or to the reaction mixture comprising the polymer) to give the thickener according to the invention. The activator is added by steps known to the person skilled in the art, for example in one or more portions, wherein optionally other components can also be added together with the activator.

A suitable polymerization initiator is used for the inverse emulsion polymerization. Preferred are redox initiators and / or thermally activatable free radical polymerization initiators.

The initiators of suitable thermally active free radicals or the oxidative component of the pair of redox initiators are mainly those of the peroxy and azo type. These include, inter alia, hydrogen peroxide, peracetic acid, t-butyl hydroperoxide, di-t-butyl peroxide, dibenzoyl peroxide, benzoyl hydroperoxide, 2-dichlorobenzoyl peroxide, 2,5-dimethyl-2, 5-bis (hydroperoxy) hexane, perbenzoic acid, t-butyl peroxypivalate, t-butyl peracetate, dilauroyl peroxide, dicapryloyl peroxide, distearoyl peroxide, dibenzoyl peroxide, diisopropyl peroxydicarbonate, didecyl peroxydicarbonate, diethosyl peroxydicarbonate , di-t-butyl perbenzoate, azobisisobutyronitrile, 2,2'-azo-bis-2,4-dimethylvaleronitrile, ammonium persulfate, potassium persulfate, sodium persulfate and sodium perphosphate.

Persulfates (peroxodisulfates), in particular sodium persulfate, are most preferred.

When the emulsion polymerization is carried out, the initiator is used in an amount sufficient to initiate the polymerization reaction. The initiator is typically used in an amount of about 0.01 to 3% in weight, based on the total weight of the monomers used. The amount of initiator is preferably from about 0.05 to 2% by weight and in particular from 0.1 to 1% by weight, based on the total weight of the monomers used.

The reverse emulsion polymerization can be carried out either as a batch process or in the form of a feeding process. In the feeding method, at least some of the polymerization initiator can be introduced as an initial charge and heated to polymerization temperature, and the remainder of the polymerization mixture is subsequently introduced, usually by a plurality of separate feeds, one or more of which comprise the monomers in pure or emulsified form, continuously or stepwise while maintaining the polymerization. Preferably, the monomer feed takes place in the form of a reverse monomer emulsion. In parallel to the monomer feed, more polymerization initiator can be dosed.

In preferred embodiments, the total amount of initiator is introduced as the initial charge, that is, there is no more initiator dosage parallel to the monomer feed.

In a preferred embodiment, the thermally activatable free radical polymerization initiator is therefore fully introduced as initial charge and the monomer mixture, preferably in the form of a reverse monomer emulsion, is introduced. Before the start of the monomer mixture feed, the initial charge is brought to the activation temperature of the thermally activatable free radical polymerization initiator or a higher temperature, but at least at 40 ° C, and the temperature corresponding remains constant. The activation temperature is considered to be the temperature at which at least half of the initiator has decomposed after one hour.

According to another preferred preparation method, the polymer is obtained by inverse emulsion polymerization of a monomer mixture in the presence of a redox initiator system. A redox initiator system comprises at least one component of oxidizing agent and at least one component of reducing agent, in which case the heavy metal ions are preferably additionally present in the reaction medium as a catalyst, for example cerium salts, salts of manganese or iron (II) salts.

Suitable oxidizing agent components are, for example, peroxides and / or hydroperoxides such as hydrogen peroxide, tert-butyl hydroperoxide, eumeno hydroperoxide, pinano hydroperoxide, diisopropylphenyl hydroperoxide, dicyclohexyl percarbonate, peroxide dibenzoyl, dilauroyl peroxide and diacetyl peroxide. Hydrogen peroxide and tert-butyl hydroperoxide are preferred.

Suitable reducing agent components are the alkali metal sulphites, alkali metal dithionites, alkali metal hyposulfites, sodium acid sulfite, Rongalit C (sodium formaldehyde sulfoxylate), mono- and dihydroxyacetone, sugars (eg, glucose or dextrose), ascorbic acid and salts thereof, acetone and bisulfite adduct and / or an alkali metal salt of hydroxymethanesulfuric acid. Sodium acid sulfite or sodium metabisulfite is preferred.

Also suitable as a component of reducing agents or catalyst are iron (II) salts, such as, eg, iron (II) sulfate, tin (II) salts, such as, eg, tin chloride (II), titanium (III) salts such as titanium (III) sulfate.

The amounts of oxidizing agent used are 0.001 to 5.0% by weight, preferably 0.005 to 1.0% by weight and in particular preferably 0.01 to 0.5% by weight, based on the total weight of the monomers used. The reducing agents are used in amounts from 0.001 to 2.0% by weight, preferably from 0.005 to 1.0% by weight and in particular preferably from 0.01 to 0.5% by weight, based on the total weight of the monomers used.

A particularly preferred redox initiator system is the sodium peroxodisulfate / sodium acid sulfite system, e.g., 0.001 to 5.0% by weight of sodium peroxodisulfate and 0.001 to 2.0% by weight of sodium acid sulfite, in particular 0.005 to 1.0% by weight of sodium peroxodisulfate and 0.005 to 1.0% by weight of sodium acid sulfite, most preferably 0.01 to 0.5% by weight of sodium peroxodisulfate and 0.01 to 0.5% by weight of sodium acid sulfite.

A very particularly preferred redox initiator system is the t-butyl hydroperoxide / hydrogen peroxide / ascorbic acid system, e.g., 0.001 to 5.0% by weight of t-butyl hydroperoxide, 0.001 to 5.0% by weight of peroxide of hydrogen and from 0.001 to 2.0% by weight of ascorbic acid, in particular 0.005 to 1.0% by weight of t-butyl hydroperoxide, 0.005 to 1.0% by weight of hydrogen peroxide and 0.005 to 1.0% by weight of ascorbic acid , most preferably 0.01 to 0.5% by weight of t-butyl hydroperoxide, 0.01 to 0.5% by weight of hydrogen peroxide and 0.01 to 0.5% by weight of ascorbic acid.

Preferably, the polymer is preferably prepared by inverse emulsion polymerization, first by preparing an aqueous phase of the water soluble components and an oil phase separately from each other. Subsequently, the two phases are mixed together to give a dispersion of water in oil. The mixture is polymerized by the addition of a redox initiator system; optionally, a thermal initiator may be added later or, if already present, thermally activated.

In the aqueous phase, preferably a chain transfer agent, an interlayer, an anionic and / or neutral monomer and optionally the associative monomer are present, and also optionally other components. Suitable additional components are, for example, complexing agents for salts such as diethylenetriaminepentaacetic acid of pentasodium.

In the oil phase, preferably an emulsifier, a stabilizer, a high-boiling oil, a low-boiling oil and / or optionally the associative monomer are present. In addition, a nonionic monomer may optionally be present in the oil phase.

Emulsifiers, stabilizers, low boiling point oils and high boiling oils as such are known to those skilled in the art. These compounds can be used individually or in the form of mixtures.

Typical emulsifiers are anionic emulsifiers, for example sodium lauryl sulfate, sodium tridecyl ether sulphates, sodium dioctyl sulfosuccinate salt and sodium salts of alkylaryl polyether sulfonates; and non-ionic emulsifiers, for example, alkyl aryl polyether alcohols and copolymers of ethylene oxide propylene oxide. Sorbitan trioleate is also suitable as an emulsifier.

Preferred emulsifiers have the following general formula: R-0- (CH2CHR '-0) n-X wherein R is C6-C30 alkyl, R 'is hydrogen or methyl, X is hydrogen or S03, M is hydrogen or an alkali metal, and n is an integer from 2 to 100.

Suitable stabilizers are described, for example, in EP-A 172 025 or EP-A 172 724. Preferred stabilizers are copolymers of stearyl methacrylate and methacrylic acid.

Suitable high-boiling oils are, for example, 2-ethylhexyl stearate and hydroheated heavy naphtha, and suitable low-boiling oils are, for example, dearomatized aliphatic hydrocarbons or low viscosity mineral oils.

In a preferred embodiment of the present invention, during component reverse emulsion polymerization component b) (at least one ethylenically unsaturated associative monomer) is also added or exclusively to the oil phase.

Further, it is preferred that, after the inverse emulsion polymerization and before the addition of activator, at least some water and at least some of the low boiling constituents are distilled from the oil phase, in particular by LDP technology medium (Polymer Technology by Liquid Dispersion). The LDP technology as such is known to those skilled in the art; it is described, for example, in WO 2005/097834.

The present invention further provides the process as such for the preparation of thickeners according to the invention in accordance with the above embodiments.

The present invention further provides acid formulations containing surfactants comprising at least one thickener according to the invention in accordance with the above definitions. The pH of the formulation is from 1 to < 7 The present invention also provides alkaline formulations containing surfactants comprising at least one thickener of the invention in accordance with the above definitions. The pH of the formulation is from 7 to 13.

Acid or alkaline formulations containing surfactant according to the invention may comprise additional ingredients known to those skilled in the art. Suitable ingredients comprise one or more substances from the group of detergents, bleach, bleach activators, enzymes, electrolytes, non-aqueous solvents, pH modifiers, fragrances, perfumes, fluorescers, dyes, hydrotropes, foam inhibitors, oils silicone, antiredeposition agents, optical brighteners, grease inhibitors, anti-shrinkage agents, anti-wrinkle agents, dye transfer inhibitors, antimicrobial active ingredients, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing auxiliaries, agents hydrophobicizing and impregnating, anti-swelling and anti-slip agents and UV absorbers.

The present invention further provides the use of an acidic formulation containing surfactant according to the invention in hair cosmetics, in hair styling, as a shampoo, as a softener, as a care composition, as a conditioner, as a skin cream, such as a shower gel, as a fabric softener for washing clothes, or as an acid detergent, preferably for toilets or toilets.

The present invention further provides the use of an alkaline formulation containing surfactant as a care composition, as a liquid detergent or as a dishwashing detergent in machine or by hand.

The present invention also provides the use of the thickener according to the invention as a viscosity modifier, for the optimization of shear thinning, as a thickening agent, for the stabilization of the suspended ingredients with a size in the range of nanometers to millimeters and / or in acidic or alkaline formulations containing surfactant.

In the description, including 'the examples, the following abbreviations are used: Monomers ACM Acrylamide AA Acrylic acid MAA Methacrylic acid NaAc Sodium acrylate BEM Behenyl-25 methacrylate MBA Methylene-bis-acrylamide (interlacing) TAAC Tetraallylammonium chloride (interlacer) NaHP Sodium hypophosphite (chain transfer agent) C16E025MAc C6-C18- (ethylene glycol) fatty alcohol methacrylate ether Others pphm Parts per hundred parts of monomers (based on components a) and b)) demin Demineralized The invention is illustrated hereinafter by the examples.

Eg emplos Comparative example Cl Synthesis of a thickener / polymer starting from anionic monomers without associative monomer, but with interleaver and chain transfer agent and also increasing the polymerization temperature.

An aqueous phase of water-soluble components is prepared by mixing the following components: 250. 24 g (139.02 pphm) of water, 0. 89 g (0.49 pphm) of pentasodium diethylenetriamine pentaacetic acid, 11. 05 g (0.06 pphm) of methylenebisacrylamide (1% in water), 180 g (100 pphm) of acrylic acid and 146. 8 g (40.78 pphm) of NaOH (50% in water) NaOH (50% in water) is used to adjust the water phase to pH 5.5.

An oil phase is prepared by mixing the following components: 20. 62 g (8.59 pphm) of sorbitan monooleate (75% in hydroheated heavy naphtha (petroleum) [Isopar G]) 93. 19 g (12.27 pphm) of a stabilizer polymeric: stearyl methacrylate-methacrylic acid copolymer (23.7% in hydroheated heavy naphtha [Isopar G]), 120. 24 g (66.8 pphm) of low viscosity mineral oil (Kristol M14) and 236. 28 g (131.27 pphm) of hydroheated heavy naphtha [Isopar G].

The two phases are mixed in a ratio of 55.6 parts of aqueous phase to 44.4 parts of oil phase with high shear to produce a water-in-oil emulsion. The resulting water-in-oil emulsion is introduced into a reactor equipped with a nitrogen spray line, stirrer and thermometer. The emulsion is purged with nitrogen, as a result of which the oxygen is removed, and cooled to 20 ° C.

The polymerization is achieved by adding a redox pair composed of 13 g (0.014 pphm) of sodium metabisulfite (0.2% in hydroheated heavy naphtha (petroleum) [Isopar G] and 13 g (0.014 pphm) of tert-butyl hydroperoxide (0.2% in heavy hydro-heated naphtha (petroleum) [Isopar G].

The redox couple is added in steps in such a way that an increase in temperature of 2 ° C / min takes place. Once the isotherm has been reached, a free radical initiator (2, 2'-azobis (2-methylbutyronitrile), CAS: 13472-08-7) it is added in 2 steps (the second step after 45 min) and the emulsion is maintained at 85 ° C for 75 minutes.

Vacuum distillation is used to remove water and low-boiling constituents of the oil phase (Isopar G).

The low viscosity mineral oil (Kristol M14) is added to the product to achieve a solids content of 54%. ? this product 8% (based on the total mass fraction of this product) of an alcohol alkoxylate containing fat (C12 / 15 alcohol alkoxylate [Synperonic 87K ™]) is added to produce a thickener (dispersion) with 50% of polymer solids fraction. The ratio of activator to polymer is therefore 16.0: 100 [% by we /% by we].

Example 1 Thickeners / polymers from anionic monomers with associative monomer and constant polymerization temperature: Example 1.1 An aqueous phase of water-soluble components is prepared by mixing the following components: 246. 13 g (140.65 pphm) of water, 0. 86 g (0.49 pphm) of pentasodium diethylenetriaminepentaacetic acid, 174. 13 g (99.5 pphm) of acrylic acid and 154. 26 g (44.07 pphm) of NaOH (50% in water) NaOH (50% in water) is used to adjust the water phase to pH 5.5.

An oil phase is prepared by mixing the following components: 20. 05 g (8.59 pphm) of sorbitan monooleate (75% in hydroheated heavy naphtha (petroleum) [Isopar G]) 90. 6 g (12.27 pphm) of polymeric stabilizer: copolymer of stearyl methacrylate-methacrylic acid (23.7% in hydroheated heavy naphtha [Isopar G]), 119. 03 g (68.02 pphm) of low viscosity mineral oil (Kristol M14) and 229. 72 g (131.27 pphm) of hydroheated heavy naphtha [Isopar G] 1. 09 g (0.5 pphm) of associative monomer: 60% by we of C16E025M7Ac: included in the commercial product Plex 6954-0 (with 20% by we of methacrylic acid / 20% by we of water).

The two phases are mixed in a ratio of 55.6 parts of aqueous phase to 44.4 parts of oil phase with hshear to produce a water-in-oil emulsion. The resulting water-in-oil emulsion is introduced into a reactor equipped with a nitrogen spray line, stirrer and thermometer. The emulsion is purged with nitrogen while heating to 50 ° C, as a result of which the oxygen is removed.

Polymerization is achieved by adding a redox pair composed of 13. 6 g (0.016 pphm) of sodium metabisulfite (0.2% in water) and 13. 6 g (0.016 pphm) of tert-butyl hydroperoxide (0.2% in water).

The redox pair is added at 50 ° C during the course of 2 hours. After this, the mixture is heated to 85 ° C and then, in 2 steps, (the second step after 45 min) a free radical initiator (2,2'-azobis (2-methylbutyronitrile), CAS: 13472- 08-7) is added and the emulsion is maintained at 85 ° C for 75 minutes.

Vacuum distillation is used to remove water and low-boiling constituents of the oil phase (Isopar G).

The low viscosity mineral oil (Kristol M14) is added to the product to achieve a solids content of 54%. To this product 8% (based on the total mass fraction of this product) of an alcohol-containing alcohol alkoxylate (C12 / 15 alcohol alkoxylate [Synperonic 87K ™]) is added to produce a thickener (dispersion) with 50% alcohol. % fraction of polymer solids. The ratio of activator to polymer is therefore 16.0: 100 [% by we /% by we].

The following examples according to table 1 are prepared as in example 1.1 taking into consideration the established changes in the monomer composition. The associative monomer C16E025MAc is added to the oil phase. The commercial product Plex 6954 O is used; it comprises 60% by weight of associative monomer and, as a solvent, water and MAA in the ratio of about 1: 1. The weight data in Table 1 refer to the amount of associative monomer without solvent. The ratio of activator to polymer in all examples according to Table 1 is in each case 16.0: 100 [% by weight /% by weight]; unless otherwise indicated, the respective thickeners (dispersion) have 50% polymer solids fraction.

Table 1 Comparative example 2 Thickeners / polymers starting from anionic monomers with associative monomer and also increasing the polymerization temperature: The following examples according to table 2 are prepared as in the comparative example Cl taking in consideration of the changes established in the monomer composition. The associative monomer C16E025 Ac is added to the oil phase. The commercial product Plex 6954 0 is used; it comprises 60% by weight of associative monomer and, as a solvent, water and MAA in the ratio of approximately 1: 1. The weight data in table 2 refer to the amount of associative monomer without solvent. The ratio of activator to polymer in all examples according to Table 2 is in each case 16.0: 100 [% by weight /% by weight]; unless otherwise indicated, the respective thickeners (dispersion) have 50% polymer solids fraction.

Table 2 General measurement methods: Unless otherwise indicated, the following general measurement methods are used in the following examples: Determination of viscosity Taking into consideration the procedures In accordance with DIN 51550, DIN 53018, DIN 53019, the Brookfield viscometer model DV II is used, unless otherwise indicated in. the following tables at a speed of 20 revolutions per minute with spindle No. 6, to measure the viscosities indicated in mPa * s.

Determination of shear dilution The measurement is carried out in a rotating rheometer ASC (automatic sample changer) of Antonpaar, with the cylinder geometry CC27, the radius of the measuring body of 13.33 mm and the radius of the measuring cup of 14.46 mm. The measurement temperature is 23 ° C. Samples are measured at continuous state shear stress starting at a low shear stress that increases at high shear stress (0.01 s'1 - 1000 s'1) and back (1000 s "1 - 0.01 s-1).

Example 3 Use of thickeners / polymers in water The thickeners are slowly added to distilled water according to Table 3 at room temperature and stirred until the formulation is homogenized. The resulting aqueous formulations comprise, according to Table 3, either 1.0% by weight of polymer at 99.0% by weight of water or 1.51% by weight of polymer at 98.5% by weight of water. The results are summarized in table 3.

Table 3 Rheology of thickeners / polymers starting from anionic monomers in water, doctors 5 minutes after preparing the formulation If the associative monomer is incorporated into the polymer, then the thickening performance increases considerably.

The process at a constant polymerization temperature of 50 ° C produces, for an otherwise identical monomer composition, an increased thickening efficiency as compared to the process with increasing polymerization temperature. The last four examples of table 3 refer to polymers containing acrylamide.

Example 4 Use of thickeners / polymers in standard formulations of fabric softener W3 W3: Preparation of a methyl ester (hydroxyethyl) ammonium ester-di-tal fatty acid methosulfate, Fabric softener partially hydrogenated (5.5% active fraction): The fabric softener has a pH of 2.7 and comprises 5.5% by weight of methyltris (hydroxyethyl) ammonium ester-di-tallow fatty acid methosulfate, (partially hydrogenated) and 94.5% by weight of deionized water.

Adding the thickener to the W3 fabric softener formulation: The thickeners according to Examples 1 and 2 and the comparative examples are slowly added, at room temperature, to the respective fabric softener formulation and stirred until the formulation has been homogenized.

The Brookfield viscosity is measured one day after the preparation. The results are summarized in Table 4.

Table 4: Thickening performance in fabric softener W3 Rheology of fabric softeners comprising thickeners / polymers starting from neutral monomers: The process at a constant polymerization temperature of 50 ° C produces, with the associative monomer or an otherwise identical monomer composition, an increased thickener yield in the W3 fabric softener formulation as compared to the polymerization temperature process. growing.

Example 5 In Table 5 below, the storage stability of the thickeners according to the invention is investigated. It is found that the thickeners according to the invention are considerably more stable.

Table 5: Storage stability of thickeners / polymers starting from anionic monomers: Significant improvement, that is, reduction of ediment, by thickeners according to the invention

Claims (19)

1. A thickener that can be prepared by a process where a polymer is obtained by a reverse emulsion polymerization of a) at least one ethylenically unsaturated monomer, soluble in water, comprising at least one anionic monomer and / or at least one non-ionic monomer, b) at least one ethylenically unsaturated associative monomer, c) optionally at least one interleaver, d) optionally at least one chain transfer agent, wherein the temperature during the inverse emulsion polymerization is kept constant and is at least 40 ° C, preferably 50 to 90 ° C, and when the inverse emulsion polymerization is completed, the activator is added giving the thickener and wherein the Thickener contains at least one activator and the activator is a surfactant.

2. The thickener according to claim 1, wherein, after the inverse emulsion polymerization and before the activator is added, at least some water and at least some of the low-boiling constituents are distilled from the oil phase.

3. The thickener in accordance with the claim 1 or 2, wherein the process is based on LDP (liquid dispersion polymer) technology.

4. The thickener according to any one of claims 1 to 3, wherein, during the reverse emulsion polymerization, component b) is added to the oil phase.

5. The thickener according to any one of claims 1 to 4, wherein the activator is selected from fatty alcohol alkoxylates, alkyl glucosides, alkylcarboxylates, alkylbenzene sulfonates, secondary alkan sulfonates and fatty alcohol sulfates, preferably selected from fatty alcohol alkoxylates.

6. The thickener according to any of claims 1 to 5, wherein a mixture of at least 2 activators is used, wherein at least one activator has a HLB value (hydrophilic-lipophilic equilibrium value) of > 12 to 20 and at least one activator has an HLB value of 1 to 12.

7. The thickener according to any of claims 1 to 6, wherein the polymer is present in the oil phase in dispersed form, preferably as a reverse dispersion, dispersion of water in oil, or as anhydrous polymer dispersed in oil.

8. The thickener according to any of claims 1 to 7, wherein in the polymer, the component a) comprises at least one anionic monomer, wherein the anionic monomer is selected from acrylic acid, methacrylic acid, itaconic acid, maleic acid, or a salt thereof, in particular the anionic monomer is Na acrylate.

9. The thickener according to any one of claims 1 to 8, wherein the water-soluble fractions of the polymer are more than 25% by weight (based on the total weight of the polymer).

10. The thickener according to any one of claims 1 to 9, wherein in the polymer, component a) comprises at least one nonionic monomer, wherein the nonionic monomer is selected from N-vinylpyrrolidone, N-vinylimidazole or a Composed in accordance with formula (I) where R7 is H or C 1 -C 4 alkyl, RQ is H or methyl, and R9 and Rio * independently of one another, are H or Ci-C30 alkyl.

11. The thickener according to any of claims 1 to 10, wherein in the polymer, the ethylenically unsaturated associative monomer (component b) is selected from a compound according to formula (II) R-0- (CH2-CHR '-0) n-CO-CR "= CH2 (II) where R is C6-C5alkyl, preferably alkyl of in particular C16-C30alkyl, R 'is H or C1-C4 alkyl, preferably H, R "is H or methyl, n is an integer from 0 to 100, preferably 3 to 50, in particular 25.

12. The thickener according to any of claims 1 to 11, wherein, in the polymer, the interleaver (component c) is selected from divinylbenzene; tetraallylammonium chloride; allyl acrylates; allyl methacrylates; diacrylates and dimethacrylates of glycols or polyglycols; butadiene; 1, 7-octadiene, allyl acrylamides or allylmethacrylamides; bisacrylamidoacetic acid; N, N'-methylenebisacrylamide or polyallyl polyol ethers such as polyallyl sucrose triallyl ether or pentaerythritol.

13. The thickener according to any of claims 1 to 12, wherein, in the polymer, the chain transfer agent (component d) is selected from mercaptans, lactic acid, formic acid, isopropanol or hypophosphites.

14. The thickener according to any of claims 1 to 13, wherein the ratio of activator to polymer is > 10: 100 [% by weight /% by weight].

15. An acidic surfactant containing formulation comprising at least one thickener according to any one of claims 1 to 14, wherein the pH of the formulation is 1 to < 7

16. The use of an acidic formulation containing surfactant according to claim 15 in hair cosmetics, in hair styling, as a shampoo, as a softener, as a care composition, as a conditioner, as a cream for the skin, as a shower gel, as a fabric softener for laundry or as an acid cleaner, preferably for the toilet or bathroom.

17. An alkaline formulation containing surfactant comprising at least one thickener according to any one of claims 1 to 14, wherein the pH of the formulation is 7 to 13.

18. The use of an alkaline formulation containing surfactant according to claim 17 as a care composition, as a liquid detergent or as a dishwashing detergent for machine washing or hand washing.

19. The use of a thickener according to any of claims 1 to 14 as a viscosity modifier, to optimize shear thinning, as a thickening agent, to stabilize suspended ingredients with a size in the range of nanometers to millimeters and / or in acidic or alkaline formulations containing surfactant.